Phosphate esters of homophthalimides

ABSTRACT

Phosphate ester derivatives of N-substituted homophthalimides form a new class of insecticides. They are highly effective against the Mexican Bean Beetle, Southern Armyworm and Spider Mite in standard insecticide dip test methods. They are highly effective against the Housefly and Bean Aphid in standard insecticide spray test methods. They are also highly effective against the Southern Corn Rootworm in the standard insecticide soil mix test method.

United States Patent 91 n 3,714,169 Gough 1 Jan. 30, 1973 [54] PHOSPHATEESTERS OF OTHER PUBLICATIONS HOMOPHTHALIMIDES v l-larriman et al. Jour.Am. Chem. Soc. Vol. 67 p. [75] Inventor: Stanley T. D. Gough, Edison,NJ. 1481, (1945) [73] Assrgnee: M0bll0|lCorporat10n Primary ExaminerDonald G. Daus [22] Filed: March 4, 1970 Att0meyOsw,ald G. Hayes, AndrewL. Gabo'riault pp No: 16,588 and Mitchell G. Condos [57] ABSTRACT [52]"260/283 260/281 Phosphate ester derivatives of N-substituted 5] I Cl C7d 30 homophthalimides form a new class of insecticides. are effectiveagainst the Mexican Bean 1 0 can 60/ 3 281 Beetle, Southern Armyworm andSpider Mite in standard insecticide dip test methods. They are highlycf- [56] References fective against the Housefly and Bean Aphid in stan-UNITED STATES PATENTS dard insecticide spray test methods. They are alsohighly effective against the Southern Corn Rootworm 2,545,283 3/1951Johnson ..260/28l in the standard insecticide soil mix test method.3,114,761 12/1963 Price 3,312,706 4/1967 Rigterink ..260/281 3 Claims,No Drawings PHOSPHATE ESTERS F HOMOPIITHALIMIDES BACKGROUND OF THEINVENTION Field of the Invention This invention is directed to novelphosphate ester insecticides. More particularly, it is concernedwithphosphate ester derivatives of N-substituted ho'rnophthalimides andtheir use as highly effective insecticides.

SUMMARY OF THE INVENTION This invention provides compounds having theformula secticides; and insecticidal composition comprising at least onesuch compound and a carrier therefor.

DESCRIPTION OF SPECIFIC EMBODIMENTS As will be noted from the formula,the compounds of this invention are phosphate ester derivatives ofN-substituted homophthalimides. Non-limiting examples of the compoundsof this invention include:

0,0-diethyl-O-3-(N-ethyl-isoquinolin-l-on)yl thiophosphate; I0,0-diethyl-0-3-(isoquinolin-1-on)yl thiophosphate;0,0-diethy1-0-3-(N-ethyl-isoquinolin-l-on)y1 phosphate;0,0-diethyl-O-3-(N-ethyl-4-ethyl-isoquinolin-l -on)y1 thiophosphate;0,0-diethyl-O-3-(N-ethyl-4-chloro-isoquinolin-lon)y1thiophosphate;0,0-diethyl-0-3-(N-ethyI-4-cyan0-isoquinolin-1- on)yl thiophosphate;0,0-diethyl-0-3-(N-ethyl-4,7-dichloro-isoquinolin-1- on)ylthiophosphate; 0,0-diphenyl-0-3-(N-phenyl-isoquinolin-1-on)y1thiophosphate; 0,0-dimethyl-0-3-(N-methyl-isoquinolin-1-on)y1thiophosphate; 0,O-dimethyl-0-3-(N methyl-4-chloro-isoquinolin-1- on)ylthiophosphate; 0,0-dimethyl-0-3-(N-methyl-4-chloro-isoquinolin-1- on)ylphosphate; and 0,0-diethyl-0-3-(N-methyl-4-ch1oro-isoquinolin-1- on)ylphosphate.

The compounds of the present invention are readily prepared by thegeneral procedure: An appropriate N- substituted homophthalimide isreacted with sodium in ethanol to give the sodium salt of thehomophthalimide. The sodium salt of the homophthalimide is then reactedwith an appropriate phosphorochloridothionate in benzene to yield anoily product upon refluxing, separating and evaporating.

The appropriate N-substituted homophthalimide is v easily prepared bythemethod of J.A.C.S. 67, 1481, 1945, in which a homophthalic acid isreacted with an appropriate amine. Other appropriate starting materialsaredisclosed by the following references:

(1) Academie Des Sciences, June 1959, pages 3568 to 3570; (2) Journal ofthe Chemical Society, 1937, pages 1312 to 1314; (3) Comp. Rend. Vol.246, 1956, pages 3255 to 3257; (4) Journal of the Chemical Society,1956, pages 2477 to 2481; (5) Journal of the Chemical Society, 1955,pages 3518 to 3521; and (6) Journal of the Chemical Society (U.S. S.R.)V01. 16, 1946, pages 301 to 307 (Chemical Abstracts, Vol. 41: 425F).

The following examples demonstrate the typical procedures.

EXAMPLE 1 N-ethyl-homophthalimide (J.A.C.S. 67, 1481, 1945 30.0 g. ofhomophthalic acid was added to ml. of 70 percent aqueous ethylamine. The'solution was heated to 180C. and evaporated. Cooling andrecrystallization from aqueous acetic acid gave 20.0 g. of product witha melting point of 103-104C.

EXAMPLE 2 0,0-diethy1-0-3-(N-ethyl-isoquinolin-1-on)yl thiophosphate16.0 g. of N-ethyl-homophthalimide was added to a solution of 1.9 g.sodium in ml. of ethanol. The solution was refluxed for 2 hours, thencooled and evaporated to give 18.1 g. of the sodium salt of thehomophthalimide.

' ON; N

NaOEt by its NMR spectrum, having a triplet at 8.65'r, .1 7

cps, (POCH Cl-l a triplet at 8.581, J 7 cps (N- CH CH a quartet at 5957,J 7 cps (N-Cl-l CH a multiplet at 5.731, (POCl-I CI-l and a multiplet at2.5-r, (ring protons). The integration of the NMR spectrum wascommensurate with the assigned structure.

A particularly suitable embodiment of the present invention is thecompound 0,0 diethyl-0-3-(N-ethylisoquinolin-1-on)yl thiophosphate. Thatis an'embodiment used for illustrating this invention as set forth inthe activity shown by such a-compound in the results of insecticidaltests set forth in the Table following the test descriptions.

INSECTICIDE TESTING METHODS DIP'TEST Mexican Bean Beetle Epliachnavarivestis Mulsant,

Lima bean leaves of uniform size are momentarily l Two-Spotted SpiderMiteTetranychus telarius Linnaeus Infested trifoliate bean leaves(Henderson bush line) are selected that have as many as adult mites perleaf. Leaves with mites attached are momentarily' dipped into a 500 ppmemulsion, solution, or suspen- -'sion of the test compounded and thenplaced (petiole only) in a 4. oz bottle of water for observation. Percent mortality is observed after 72 hours.

SPRAY TESTS Housefly Musca domestica Linnaeus Adult houseflies arecontained in 100 mm. petri dish screened cages and exposed to a spray of10 ml. acetone solution of test compound. A concentration of 500 ppm isused, with 10 flies in each cage. Per cent mortality is observed after24 hours. Bean Aphid Aphisfabae This test is conducted in a mannersimilar to that used for the housefly. The test specimens are Nasturtiumleaves'infested with bean aphids.

SOIL MIX TEST Southern Corn Rootworm Prior to treatment, a mixture of 2parts soil and 1 part sand is air dried for 2 or 3 days and screened 1through a 20 mesh sieve. 90g. of this is mixture is placed into l0 oz.waxed cups. 10 ml of a 30 ppm water-acetone solution of the testmaterial is pipetted onto the soil and the cup is capped.

After I to 2 hours the cups are vigorously shaken.

Two corn seedlings are placed near the bottom of the cup in the soilmixture and 5 second to third instar root-- worm larvae are placed onthe soil surface. The cups are again capped. Each treatment isreplicated 2 times.

Per cent mortality is observed after 5 days.

I TABLE 500 PPM Mexican Southern Two-Spotted Bean Bean Beetle ArmywormSpider Mite Housefly Aphid I00 I00 I00 Southern Corn Rootworm I00 (at 30ppm) From the data in this table, it will be noted that the phosphateester derivatives of N-substituted homophthalimides, specifically forpurposes of demonstrating the insecticidal activity of the particularlysuitable embodiment of Example 2, have a broad range of insecticidalactivity. They are 100 percent effective against all insect speciestested in contact dip, spray,

and soil mix tests.

The compounds of this invention have been found i6 exhibit considerablebiological activity and are espe cially potent insecticides when usedagainst important agricultural pests. These compounds may be used invarious ways to achieve biological action. They can be applied per se,as solids or in vaporized form, but are preferably applied as the toxiccomponents in insecticidal compositions of the compound and a carrier.

, The compositions can be applied as dusts, as liquid sprays, or asgas-propelled sprays and can contain, in addition to a carrier,additives such as emulsifying agents, wetting agents, binding agents,gases compressed to the liquid state, odorants, stabilizers and thelike. A wide variety of liquid and solid carriers can be used in theinsecticidal compositions. Non-limiting examples of liquid carriersinclude water; organic solvents such as alcohols, ketones, amides andesters; mineral oils such as kerosene, light oils, medium oils; andvegetable oils such as cottonseed oil. Nonlimiting examples of solidcarriers include talc, bentonite,,

diato'm'aceous earth, pyrophyllite, fullers earth, gypsum,flours derivedfrom cotton seeds and'nut shells, and various natural and syntheticclays having a pH not exceeding about 9.5.

The amount of the compounds of this invention util ized in insecticidalcompositions will vary rather widely. It depends to some extent upon thetype of composition in which the material is being used, the nature ofthe condition to be controlled, and the method of application (i.e.,spraying, dusting, etc.,). In the ultimate insecticidal composition, asapplied in the field, insecticide concentrations as low as 0.0001'weight per cent of the total composition can be used. In general,compositions, as applied, containing about 0.05 weight per centinsecticide in eitherliquid or solid carrier give excellent results. Insome case, however, stronger dosages up to about 10 weight per cent maybe required.

In practice, insecticidal compositions are usually prepared in the formof concentrates, which are diluted .in the field to the concentrationdesired for application. For example, the concentrate can be a wettablepowder containing large amounts of a compound of this invention, acarrier (e.g., attapulgite or other clay), and

wetting and dispersing agents. Such a powder can be diluted prior toapplication, by, dispersing it in water to obtain a sprayable suspensioncontaining the concentration of insecticide desired for application.Other concentrates can be solutions that can be later diluted, e.g.,with kerosene. Thus, it is within the contemplation of this invention toprovide insecticidal compositions containing up to about per cent, byweight of the composition, of an insecticidal compound of thisinvention. Accordingly, depending upon whether it is ready forapplication or it is in concentrated form, the contemplated insecticidalcompositions contain between about 0.0001 per cent and about 80 percent, by weight of the composition, of an' insecticidal compound of thisXOR wherein R is alkyl (C -C alkenyl (C -C alkynyl (C -C4) or phenyl, Ris OR, R" is hydrogen or R, X is oxygen or sulfur, W is hydrogen,halogen, nitro, R, R, COOR, COR, and n is l.

2. A compound as defined in claim 1, wherein R is alkyl (C -C R is OR,R" is R, X is sulfur, and W is hydrogen.

3. The compound as defined in claim 1 having the following structure:

1. A compound having the formula:
 2. A compound as defined in claim 1,wherein R is alkyl (C1-C3), R'' is OR, R'''' is R, X is sulfur, and W ishydrogen.